17185-29-4Relevant articles and documents
Abatjoglou, Anthony G.,Bryant, David R.
, p. 932 - 934 (1984)
Action of triphenylphosphine on [Rh(HCOO)(PPh3) 2(CO)]. A novel synthetic route to [HRh(PPh3) 3(CO)]
Varshavsky, Yuri S.,Cherkasova, Tatiana G.,Podkorytov, Ivan S.
, p. 489 - 491 (2004)
Rhodium(I) carbonyl formato complex, trans-[Rh(HCOO)(PPh3) 2(CO)], on heating in propanol-2 in the presence of excess triphenylphosphine converts into carbonyl hydride complex, [HRh(PPh 3)3(CO)], with a good yield. The reaction provides a new and attractive method of synthesis of [HRh(PPh3)3(CO)].
The crystal and molecular structure of a new polymorph of carbonylhydridotris(triphenylphosphine)rhodium(I) having a Rh-H stretching absorption at 2013 cm-1
Babra, I. S.,Morley, L. S.,Nyburg, S. C.,Parkins, A. W.
, p. 997 - 1000 (1993)
A new polymorph of HRh(CO)(PPh3)3, with a υRh-H of 2013 cm-1, has been isolated by crystallization from tert-butyl methyl ether/tetrahydrofuran.The crystals are monoclinic (space group P21/n), with a=21.48(2) Angstroem, b=14.92(2) Angstroem, c=14.52(1) Angstroem, β=107.95(8) deg.A final R value of 0.065 was obtained using 2243 reflections which had Inet > 2.5?(Inet).The structure of the new polymorph has a similar coordination geometry to the known polymorph, but a different conformation of one of the phenyl rings.
Hydroformylation of Alkenes in a Planetary Ball Mill: From Additive-Controlled Reactivity to Supramolecular Control of Regioselectivity
Cousin, Kévin,Menuel, Stéphane,Monflier, Eric,Hapiot, Frédéric
supporting information, p. 10564 - 10568 (2017/08/22)
The Rh-catalyzed hydroformylation of aromatic-substituted alkenes is performed in a planetary ball mill under CO/H2 pressure. The dispersion of the substrate molecules and the Rh-catalyst into the grinding jar is ensured by saccharides: methyl-α-d-glucopyranoside, acyclic dextrins, or cyclodextrins (CDs, cyclic oligosaccharides). The reaction affords the exclusive formation of aldehydes whatever the saccharide. Acyclic saccharides disperse the components within the solid mixture leading to high conversions of alkenes. However, they showed typical selectivity for α-aldehyde products. If CDs are the dispersing additive, the steric hindrance exerted by the CDs on the primary coordination sphere of the metal modifies the selectivity so that the β-aldehydes were also formed in non-negligible proportions. Such through-space control via hydrophobic effects over reactivity and regioselectivity reveals the potential of such solventless process for catalysis in solid state.
Ethylene hydroformylation in imidazolium-based ionic liquids catalyzed by rhodium-phosphine complexes
Diao, Yanyan,Li, Jing,Wang, Ling,Yang, Pu,Yan, Ruiyi,Jiang, Li,Zhang, Heng,Zhang, Suojiang
, p. 54 - 62 (2013/02/23)
In this research, the catalytic activity of a rhodium-based (Rh) catalyst with imidazolium-based ionic liquids (IBILs) as solvents for ethylene hydroformylation was studied. The structures of IBILs had an important influence on the activity and stability of the Rh catalyst. The IBILs with longer cation side chains, which were the strong steric hindrances around the Rh catalyst, were more unfavorable for the catalytic activity. The turnover frequency (TOF) of the Rh catalyst was 10627 h-1 when [Bmim][BF4] was used as solvent. The activity of the Rh complexes in the ionic liquid is better than they do in toluene. We used electrospray ionization mass spectrometry to characterize the catalyst after the reaction and found that [Bmim]+ acts as a ligand of the Rh catalyst to form a new active catalytic site [Rh(CO)(PPh3)2(Bmim)(BF4)]+ through the coordination of the Rh atom with the imidazole-2-C group of [Bmim][BF 4], and it was essential for the stabilization of the Rh catalyst and prevented the formation of low-active Rh clusters. In addition, the catalyst recycling test showed that the Rh catalyst could be reused with [Bmim][BF 4] as solvent without obvious loss of catalytic activity.
